CN107004806A - High-fire resistance and anti-flammability barrier film and electrochemical cell - Google Patents
High-fire resistance and anti-flammability barrier film and electrochemical cell Download PDFInfo
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- CN107004806A CN107004806A CN201580046070.3A CN201580046070A CN107004806A CN 107004806 A CN107004806 A CN 107004806A CN 201580046070 A CN201580046070 A CN 201580046070A CN 107004806 A CN107004806 A CN 107004806A
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/443—Particulate material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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Abstract
One embodiment of the present invention provides a kind of barrier film, including：Porous substrate；With porous refractory layer, it is formed at the one or both sides of the porous substrate and comprising adhesive, described adhesive includes macromolecule resin, the macromolecule resin includes the repeat unit containing the first component and the second component, first component contains phosphate or phosphonate, and second component contains nitrogen.
Description
Technical field
The present invention relates to the barrier film of high-fire resistance and anti-flammability and the electrochemical cell including the barrier film.
Background technology
Electrochemical cell barrier film (separator) refers to make in battery to continue while positive pole and mutually isolated negative pole
Property ionic conductance is maintained so that the intermediate coat that the charging and discharging of battery can be carried out.
Recently, along with the lightweight of the electrochemical cell for the portability that improves electronic equipment and inclining for miniaturization
To occurring needing the tendency for the high-power high capacity cell in electric automobile etc..Used for above-mentioned high-power Large Copacity
It is secondary for providing powerful lithium compared with capacity in terms of the element cell (battery cell) of the medium-and-large-sized battery pack on way
Battery, has carried out many research.
Due to foregoing diversified advantage, lithium secondary battery is to have as the element cell of medium-and-large-sized battery pack
The candidate of power, but there are the following problems：In discharge and recharge, internal temperature of battery rises, and produces the decomposition reaction band by electrolyte
The imflammable gas that comes, by the reaction zone of electrolyte and electrode Lai imflammable gas, the oxygen that is brought by the decomposition of positive pole etc.,
And occur blast or occur fire.In addition, use polyolefin mesentery as secondary cell barrier film when, exist and ask as follows
Topic：At relatively low temperatures, film occurs to melt down (Korean granted patent the 10-0775310th).
Accordingly, it is desirable to provide it is a kind of electrochemical cell, particularly medium-and-large-sized capacity battery in prevent or suppress it is on fire,
The new barrier film that the original performance of battery is also improved or maintained while heat resistance obtains improving.
The content of the invention
It is an object of the present invention to provide a kind of bonding force with anti-flammability and high-fire resistance, with porous substrate and
Oxidative resistance is excellent, the dispersiveness of the inorganic particulate of porous refractory layer is improved barrier film and the electrification using the barrier film
Learn battery.
In one embodiment of the present invention there is provided a kind of barrier film, the barrier film includes：Porous substrate；And porous
Refractory layer, is formed at the one or both sides of the porous substrate, and the porous refractory layer includes macromolecule resin, the height
Molecule resin includes the repeat unit containing the first component and the second component, and first component contains phosphate or phosphonate,
Second component contains nitrogen.
In addition, another embodiment of the present invention provides a kind of electrochemical cell, the electrochemical cell is by according to above-mentioned
The barrier film of one mode is formed.
Barrier film according to an embodiment of the present invention and show following characteristic using the electrochemical cell of the barrier film：
With anti-flammability and high-fire resistance, the bonding force of porous substrate and porous refractory layer is excellent, and the dispersed of inorganic particulate is obtained
To improvement, oxidative resistance is excellent.
Brief description of the drawings
Fig. 1 is the three-dimensional exploded view of the electrochemical cell according to an embodiment.Electrochemical cell 100 includes：Electrode group
Part 40, makes barrier film 30 between positive pole 10 and negative pole 20 and winds to form；With housing 50, built with above-mentioned electrode assemblie 40.
Above-mentioned positive pole 10, above-mentioned negative pole 20 and above-mentioned barrier film 30 are impregnated in electrolyte (not shown).
Embodiment
According to an embodiment of the present invention there is provided a kind of barrier film, the barrier film includes：Porous substrate；And porous
Refractory layer, is formed at the one or both sides of the porous substrate, and the porous refractory layer includes macromolecule resin, the height
Molecule resin includes the repeat unit containing the first component and the second component, and first component contains phosphate or phosphonate,
Second component contains nitrogen.
Above-mentioned porous substrate has multiple stomatas, can use the porous base that can be used generally for electrochemical element
Material.Can be selected from without limitation by polyethylene, polypropylene, polyethylene terephthalate, poly- as porous substrate
It is mutual-phenenyl two acid bromide two alcohol ester, polyester, polyacetals, polyamide, polyimides, makrolon, polyether-ether-ketone, PAEK, poly-
Etherimide, polyamidoimide, polybenzimidazoles, polyether sulfone, polyphenylene oxide, cyclic olefine copolymer, polyphenylene sulfide and polyethylene
Any macromolecule or the polymeric membrane that is formed by the two or more mixtures in these macromolecules in the group of naphthalene composition.Make
For an example, above-mentioned porous substrate can also be polyolefin base material, polyolefin base material open circuit (shut down) function
It is excellent, it is favorably improved the security of battery.Polyolefin base material can selected from for example by polyethylene monofilm, polypropylene monofilm,
The three of the duplex film of polyethylene/polypropylene, polypropylene, polyethylene/polyacrylic triple films and polyethylene/polypropylene/polyethylene
The group of weight film composition.As another example, polyolefin-based resins can also include non-olefinic resin outside olefin resin, or
Person includes the copolymer of alkene and non-olef iotanic monomers.The thickness of above-mentioned porous substrate can be 1 μm~40 μm, it is more specific for
It can be 5 μm~15 μm, more specifically can be 5 μm~10 μm.When using the porous substrate in above-mentioned thickness range,
It can produce with appropriate thickness, i.e. both sufficiently thick to the positive pole that can prevent battery and the degree of negative pole short circuit, not have again
There is the thick barrier film to the increased degree of internal resistance for making battery.
Above-mentioned porous refractory layer can include macromolecule resin, and the macromolecule resin is included containing the first component and the
The repeat unit of two components, first component contains phosphate or phosphonate, and second component contains nitrogen.At this point it is possible to
For the form of the copolymer comprising the first repeat unit and the second repeat unit, wherein, the first repeat unit contains above-mentioned first
Component, the second repeat unit contains above-mentioned second component；Or be comprising simultaneously containing above-mentioned first component and the second component
The form of the polymer of one repeat unit.Above-mentioned macromolecule resin due to prevented containing phosphate or phosphonate because
Produce oxygen for being brought by decompositions of positive pole etc. and make battery explosion or generation fire, and due to changing containing nitrogen
The kind bonding force with porous substrate, in addition, when porous refractory layer includes inorganic particulate, above-mentioned inorganic particulate can be improved
Dispersiveness.Not limited by particular theory, the phosphate comprising phosphate or phosphonate structure in barrier film can pass through
Thermally decompose to generate poly-metaphosphoric acid.The poly-metaphosphoric acid generated can form protective layer on barrier film, or in the generation of poly-metaphosphoric acid
During can separate oxygen with dehydration and the carbon overlay film that produces, so that anti-flammability can be shown.In addition, not by specific
Theoretical limitation, when containing nitrogen, can deduce can be improved and porous base by providing the localization of the unshared electron pair of nitrogen
The bonding force of material and the dispersiveness of inorganic particulate.In addition, barrier film according to an embodiment of the present invention by existing as described above
Macromolecule resin is used in porous refractory layer, above-mentioned macromolecule resin includes the repetition list containing the first component and the second component
Member, above-mentioned first component contains phosphate or phosphonate, and above-mentioned second component contains nitrogen, so as to have the advantage that in the following areas：
Even if without other adhesive, fire retardant in addition or other inorganic particulate, can also ensure and barrier film base material simultaneously
Sufficient bonding force, suppression on fire and heat resistance.
In the macromolecule resin of one embodiment of the present invention, above-mentioned first component containing phosphate or phosphonate
Example is as follows.
[chemical formula 1]
[chemical formula 2]
In above-mentioned chemical formula 1 and chemical formula 2, R1And R2Can be separately hydrogen, or selected from by substitution or non-taking
The C in generation1-6Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-20Cycloalkyl and C6-30Aryl composition group.Show as one
Example, in above-mentioned chemical formula 1 and chemical formula 2, R1And R2Can be separately hydrogen, or it is non-substituted or more than one
Halogen, OH, C1-6Alkyl, alkoxy, nitro, cyano group, carbonyl, sulfydryl substitution C1-6Alkyl, C6-30Aryl or C3-10's
Cycloalkyl.It is used as specific example, R1And R2Can be separately hydrogen, or it is non-substituted or by more than one halogen,
OH、C1-6Alkyl-substituted phenyl, naphthyl, cyclopropyl, cyclobutyl, methyl, ethyl, propyl group, butyl etc..
In the macromolecule resin of one embodiment of the present invention, the second component containing nitrogen can be containing acid imide or
The structure of acid amides.When the second component is the structure containing acid imide or acid amides, because of intermolecular imide bond or amido link
So that adhesion is stronger, therefore, it is possible to high heat-resisting with what will not also be melted down even if porous substrate at a relatively high temperature
Property.
As specific example, above-mentioned second component can be structure or carbon containing phthalimide
Atomicity is 1~10 residue containing alkylamide, the residue containing eneamide or the residue containing aryl amide.Especially
Ground, above-mentioned second component can also be the structure containing phthalimide, when above-mentioned second component is containing O-phthalic
During imido structure, the number of hydrogen atoms of amido is less and can have bigger potential window, therefore with even in high electricity
Pressure is also easy to stable without light labile advantage.
Another specific example of the second component containing nitrogen is as follows.
[chemical formula 3]
In above-mentioned chemical formula 3, R3Can be hydrogen, or selected from by substituted or non-substituted C1-6Alkyl, C2-6Alkene
Base, C2-6Alkynyl, C3-10Cycloalkyl and C6-30Aryl composition group.It is used as an example, in above-mentioned chemical formula 3, R3
Can be hydrogen, or it is non-substituted or by more than one halogen, OH, C1-6Alkyl, C2-6Alkenyl, alkoxy, nitro, cyanogen
Base, carbonyl, sulfydryl or C2-6Alkynyl substituted C1-6Alkyl, C6-30Aryl or C3-10Cycloalkyl.As specifically showing
Example, R3Can be hydrogen, or it is non-substituted or by more than one halogen, OH, C1-6Alkyl or C2-6Alkenyl substitution phenyl,
Naphthyl, cyclopropyl, cyclobutyl, cyclopenta, methyl, ethyl, propyl group, butyl, vinyl, acrylic, heptenyl or cyclobutenyl.
As another example of the second component containing nitrogen, the structure containing nitrogen-containing hetero aromatic series hydrocarbon ring can be enumerated.
In this manual, " nitrogen-containing hetero aromatic series hydrocarbon ring " refer to more than one carbon atom of aromatic hydrocarbon cycle compound replaced by nitrogen and
Into heteroaromatic hydrocarbon ring.Above-mentioned aromatic hydrocarbon cycle compound can be monocyclic, bicyclic or tricyclic structure., can as its example
With enumerate two or more nitrogen-containing hetero aromatic series hydrocarbon ring directly in conjunction with or more than one nitrogen-containing hetero aromatic series hydrocarbon ring and more than one
The structure that aromatic hydrocarbon cycle compound replaces the hydrogen in methyl and replaces to be formed.As specific example, it can enumerate
At least one carbon of at least one aromatic series hydrocarbon ring is former in Ppolynuclear aromatic hydrocarbon (poly-aromatic hydrocarbons)
The structure that son is replaced by nitrogen.
As more specifically example, the second component containing nitrogen can also be selected from following chemical formula.
As an example, the repeat unit that above-mentioned macromolecule resin can be comprising chemical formula 4 or chemical formula 5.[chemical formula
4]
[chemical formula 5]
In above-mentioned chemical formula 4 and chemical formula 5, substituent R1、R2And R3Definition with above-mentioned chemical formula 1 to 3 in substitution
Base R1、R2And R3Definition it is identical.
The glass transition temperature of above-mentioned macromolecule resin can be 180 DEG C~300 DEG C, can be specifically 200 DEG C~280
DEG C, more specifically can be 220 DEG C~250 DEG C.It is heat-resisting the macromolecule resin for meeting above range is included in into porous
In the case of barrier film in layer, due to will not also melt down at a relatively high temperature, therefore, it is possible to Gao Nairete
Property.
The weight average molecular weight of above-mentioned macromolecule resin can be in the range of 5,000~350,000, if above-mentioned
In the range of, then can be advantageously in terms of bonding force and heat resistance.
The barrier film according to another embodiment of the present invention is illustrated below.Included according to the barrier film of present embodiment
The porous refractory layer of porous substrate and formation on the porous substrate, it is in the following areas with above-mentioned according to the present invention
The barrier film of an embodiment there is difference, i.e. the porous refractory layer is in addition to macromolecule resin also comprising additional
Adhesive component, the macromolecule resin includes the repeat unit containing the first component and the second component, and first component contains
There are phosphate or phosphonate, second component contains nitrogen.Illustrated below as center, on real with an embodiment
Identical structural element in matter, detailed description will be omitted.Present embodiment is by further including additional adhesive component, not only
The bonding force with porous substrate can be further improved, and heat resistance and cycle characteristics can also be improved.
The adhesive component of above-mentioned addition for example can be Kynoar (PVdF, Polyvinylidene
Fluoride) based polymer.Kynoar based polymer can include Kynoar (PVdF, Polyvinylidene
Fluoride) homopolymer, polyvinylidene fluoride copolymer (Polyvinylidene fluoride copolymer) or they
Mixture.Above-mentioned polyvinylidene fluoride homopolymer, which refers to only include, derives from vinylidene (VDF, Vinylidene fluoride)
Repeat unit or other species in addition to the repeat unit from vinylidene comprising below 5 weight % weight
The polymer of multiple unit.Wherein, in above-mentioned polyvinylidene fluoride homopolymer, as the repeat unit of above-mentioned other species, do not include
From hexafluoropropene (HFP, Hexafluoropropylene) repeat unit.Polyvinylidene fluoride copolymer refers to except inclined
The copolymer being also polymerized simultaneously using other monomers outside PVF, is specifically referred to comprising from hexafluoropropene
Repeat unit also comprises more than 5 weights in addition to vinylidene repeat unit and from the repeat unit of hexafluoropropene
Measure the copolymer of the repeat unit of % other species.Above-mentioned polyvinylidene fluoride copolymer can include comprising from inclined fluorine second
The repeat unit of alkene and repeat unit from hexafluoropropene Kynoar-hexafluoropropene (PVdF-HFP,
Polyvinylidene fluoride-Hexafluoropropylene) based copolymer.Above-mentioned Kynoar-hexafluoropropene
Based copolymer can include Kynoar-hexafluoropropene (PVdF-HFP, Polyvinylidene fluoride-
Hexafluoropropylene) bipolymer or except the repeat unit from vinylidene and from hexafluoro third
The copolymer more than ternary of other repeat units is further comprised outside the repeat unit of alkene.It is used as the bonding of above-mentioned addition
Another example of agent component, can enumerate and be selected from by polymethyl methacrylate (polymethylmethacrylate), gather
Acrylonitrile (polyacrylonitrile), polyvinylpyrrolidone (polyvinylpyrrolidone), polyvinyl acetate
(polyvinylacetate), PEO (polyethyleneoxide), cellulose acetate (cellulose
Acetate), acetylbutyrylcellulose (cellulose acetate butyrate), cellulose acetate propionate (cellulose
Acetate propionate), cyanoethyl pullulan (cyanoethylpullulan), cyanoethyl polyvinylalcohol
(cyanoethylpolyvinylalcohol), cyanethyl cellulose (cyanoethylcellulose), cyanoethyl sucrose
(cyanoethylsucrose), amylopectin (pullulan), carboxymethyl cellulose (carboxyl methyl
) and acrylonitrile styrene-butadiene-copolymer (acrylonitrilestyrene-butadiene cellulose
Copolymer) one kind or their mixture in the group of composition.
The barrier film according to another embodiment of the present invention is illustrated below.Included according to the barrier film of present embodiment
Porous substrate and porous refractory layer, there is difference in it, i.e. above-mentioned porous with one embodiment of the present invention in the following areas
Property refractory layer further contains inorganic particulate.Illustrated below as center, on substantially the same with an embodiment
Structural element, detailed description will be omitted.According to the barrier film of present embodiment due to containing inorganic particulate, it can not only improve heat-resisting
Property, and can also be it is advantageously ensured that appropriate transmissivity is to improve the degree of ionic conductivity.
The species of inorganic particulate contained by above-mentioned porous refractory layer is not specially limited, and can be used logical in the field
The inorganic particulate often used.As the nonrestrictive example of above-mentioned inorganic particulate, Al can be enumerated2O3、SiO2、B2O3、
Ga2O3、TiO2Or SnO2Deng.They can be used alone or mix it is two or more use, it is, for example, possible to use Al2O3(oxygen
Change aluminium).Inorganic particulate in above-mentioned porous refractory layer plays an inter-species of the physical aspect for being able to maintain that porous refractory layer
The effect of parting (spacer).Thereby, it is possible to prevent the inorganic particulate in the assembling process of battery etc. in porous refractory layer
The problem of disengaging and ensure morphological stability, sufficient bonding force is not only assigned between porous refractory layer and porous substrate
So as to suppress by the contraction of thermally-induced porous substrate, but also the short circuit of electrode can be prevented, with high temperature safe
The excellent advantage of property.
The size of above-mentioned inorganic particulate is not specially limited, and average grain diameter can be 100nm~1000nm, specifically may be used
Think 300nm~600nm.When using the inorganic particulate in above-mentioned magnitude range, it can prevent porous refractory layer from combining liquid
The dispersiveness of interior inorganic particulate and coating processability reduction, and can suitably adjust the thickness of porous refractory layer.
Above-mentioned inorganic particulate be able to can specifically contain in porous refractory layer containing the weight % of 70 weight %~98
There is the weight % of 80 weight %~95.The morphological stability of barrier film is able to ensure that within the above range, not only in porous refractory layer
Sufficient bonding force is assigned between porous substrate so as to suppress by the contraction of thermally-induced porous substrate, but also
The short circuit of electrode can effectively be prevented.
The manufacture method to barrier film according to an embodiment of the present invention is illustrated below.It is real according to the one of the present invention
Applying the manufacture method of the barrier film of mode includes：The heat-resisting layer composition of the porous containing macromolecule resin and solvent is manufactured, it is described
Macromolecule resin includes the repeat unit containing the first component and the second component, and first component contains phosphate or phosphonic acids
Salt, second component contains nitrogen；Formed in the one or both sides of porous substrate using the heat-resisting layer composition of the porous
Porous refractory layer.
Specifically, above-mentioned barrier film can make it by porous substrate after the applying porous heat-resisting layer composition of property
Dry to be formed.The micropore of above-mentioned porous substrate can be formed by generally known manufacture method.As unrestricted
The example of property, it is known to which dry process and damp process, specifically, above-mentioned porous substrate can be by porous substrate groups
Compound is extruded and is extended and form micropore in porous substrate to manufacture.
The heat-resisting layer composition of porous of porous refractory layer for forming barrier film can include foregoing high score subtree
Fat and solvent, in another example, can further include inorganic particulate in above-mentioned composition.Manufacture porous refractory layer group
There is no particular restriction for the method for compound, and the heat-resisting layer composition of porous can be manufactured in the following way：Using by macromolecule
Resin is dissolved in Polymer Solution in solvent as the heat-resisting layer composition of porous；Or in above-mentioned Polymer Solution
As the heat-resisting layer composition of porous after scattered inorganic particulate；Or producing above-mentioned Polymer Solution respectively and disperseing
Have after the inorganic particulate dispersion liquid of inorganic particulate, they are together mixed with appropriate solvent.Manufacture porous refractory layer group
A kind of method of compound can include：Further mixed to macromolecule resin and solvent disclosed in this specification, or wherein
Close after inorganic particulate, stirred 30 minutes~5 hours at 10 DEG C~40 DEG C.
The solvent used in the manufacture of above-mentioned Polymer Solution and inorganic particulate dispersion liquid is if high score can be dissolved
Subtree fat and the solvent that can fully disperse inorganic particulate, then be not specially limited.It is used as what can be used in the present invention
The nonrestrictive example of above-mentioned solvent, can enumerate dimethylformamide (Dimethyl formamide), dimethyl sulfoxide (DMSO)
(Dimethyl sulfoxide), dimethyl acetamide (Dimethyl acetamide), dimethyl carbonate (Dimethyl
) or 1-METHYLPYRROLIDONE (N-methylpyrrolydone) etc. carbonate.With the weight of the heat-resisting layer composition of porous
On the basis of, the content of solvent can be the weight % of 20 weight %~99, can be specifically the weight % of 50 weight %~95, more
Can be specifically the weight % of 70 weight %~95.When the solvent containing above range, easy to manufacture porous refractory layer
Composition, and the drying process of porous refractory layer can be smoothed out.In addition, with the solid of the heat-resisting layer composition of porous into
Point gross weight on the basis of, above-mentioned macromolecule resin can for example contain 2 weight % containing the weight % of 2 weight %~100
~70 weight %.In more specifically example, the weight % of 5 weight %~30 can be contained.
In above-mentioned Polymer Solution and inorganic particulate dispersion liquid after further mixed solvent, by utilizing ball mill
The process that (Ball mill), ball mill (Beads mill) or spiral mixer (Screw mixer) etc. are sufficiently stirred for,
The porous refractory layer combination liquid of form of mixtures can be produced.
The method that porous refractory layer is formed on above-mentioned porous substrate is not specially limited, and can be used in the present invention
Technical field in commonly used approach, such as coating process, lamination (lamination), coextrusion (coextrusion).
As the nonrestrictive example of above-mentioned coating process, can enumerate leaching (Dip) coating, mould (Die) coating, roller (Roll) coating or
Comma scrapes (Comma) coating etc..They individually or can mix two or more methods to apply.The porous of the barrier film of the present invention
Refractory layer can for example be formed by dip coating.
The thickness of porous refractory layer according to the embodiment of the present invention can be 0.01 μm~20 μm, specifically may be used
Think 1 μm~15 μm.In above-mentioned thickness range, the porous refractory layer of suitable thickness can be formed to obtain excellent heat
Stability and bonding force, and the blocked up internal resistance increase so as to suppress battery of the overall thickness of barrier film can be prevented.
In embodiments of the present invention, porous refractory layer being dried can use by warm air, hot blast, low humidity
Drying or vacuum drying or irradiate the methods such as Far infrared electric beamlet that wind is carried out.Moreover, species of the drying temperature according to solvent
And it is different, it can be dried at a temperature of substantially 60 DEG C~120 DEG C.Drying time is different also according to the species of solvent,
It can dry substantially 1 minute~1 hour.In specific example, can be dried at a temperature of 90 DEG C~120 DEG C 1 minute~
30 minutes or 1 minute~10 minutes.
By the barrier film comprising porous refractory layer described in embodiments of the present invention placed at 200 DEG C 30 minutes it
Longitudinal direction (MD, Machine Direction) or the percent thermal shrinkage of horizontal (TD, Transverse Direction) afterwards is respectively
Less than 10%, it can be specifically less than 5%, more specifically can be less than 3%.Within the above range, with effective
Prevent electric pole short circuit and improve the advantage of battery security.
The method that the percent thermal shrinkage of above-mentioned barrier film is measured is not specially limited, the technology in the present invention can be used
Commonly used approach in field.
The nonrestrictive example for the method being measured to the percent thermal shrinkage of barrier film is as follows.I.e., it is possible to using such as lower section
Formula is carried out：Manufactured barrier film is cut off with width (MD) about 5cm × length (TD) about 5cm size, by its chamber at 200 DEG C
(chamber) after being taken care of 30 minutes in, the shrinkage degree in MD directions and TD directions to above-mentioned barrier film is measured, and is calculated
Percent thermal shrinkage.
The anti-flammability of the barrier film comprising porous refractory layer described in embodiments of the present invention hinders according to UL94VB
Can be more than V0 excellent anti-flammability grade when combustion regulation is measured.Within the above range, can effectively prevent it is above-mentioned every
The burning of film, therefore, it is possible to improve the security of battery.
The method that anti-flammability to above-mentioned barrier film is measured is not specially limited, and the technology in the present invention can be used to lead
Commonly used approach in domain.
The nonrestrictive example for the method that anti-flammability to above-mentioned barrier film is measured is as follows.That is, will be manufactured
10cm × 50cm barrier film is folded into after 10cm × 2cm, fixes top and the bottom to manufacture test film, according to UL94VB, resistance
Combustion property grade is measured on the basis of test film burning time.
The air penetrability of the barrier film comprising porous refractory layer described in embodiments of the present invention can be 400sec/
Below 100cc, can be specifically below 310sec/100cc, more specifically can be below 280sec/100cc.
In above range, the flowing of the ion and electronics of the inside battery comprising above-mentioned barrier film is smooth, can improve battery performance.
The method that the air penetrability of above-mentioned barrier film is measured is not specially limited, the technology in the present invention can be used to lead
Commonly used approach in domain.
The nonrestrictive example for the method being measured to the air penetrability of above-mentioned barrier film is as follows.That is, to it is manufactured every
Film, air penetrability is tried to achieve by the way of being measured to 100cc air by the time needed for barrier film.
According to another embodiment of the invention there is provided a kind of electrochemical cell, the electrochemical cell includes this explanation
Porous separator and positive pole, negative pole disclosed in book, and filled up by electrolyte, the porous separator includes including macromolecule
The porous refractory layer of resin, the macromolecule resin includes the repeat unit containing the first component and the second component.
The species of above-mentioned electrochemical cell is not specially limited, and can be the Known Species in the technical field of the present invention
Battery.
Above-mentioned electrochemical cell according to an embodiment of the present invention can be specifically the secondary electricity of such as lithium metal
The lithium secondary battery of pond, lithium rechargeable battery, lighium polymer secondary battery or lithium ion polymer secondary cell etc..
The method of the electrochemical cell of manufacture according to an embodiment of the present invention is not specially limited, and can be used at this
Commonly used approach in the technical field of invention.
Fig. 1 is the three-dimensional exploded view of the electrochemical cell according to an embodiment.On the electrification according to an embodiment
Battery is learned, enumerates and illustrates exemplified by rectangular electrochemical cell, but the present invention is not limited to this, but can apply to
The battery of the diversified forms such as lithium polymer battery, cylindrical battery.
Referring to Fig. 1, the electrochemical cell 100 involved by an embodiment includes：Electrode assemblie 40, by barrier film 30 between just
Between pole 10 and negative pole 20 and wind form；With housing 50, built with above-mentioned electrode assemblie 40.Above-mentioned positive pole 10, above-mentioned negative pole
20 and above-mentioned barrier film 30 be impregnated in electrolyte (not shown).
Above-mentioned barrier film 30 is as previously described.
Above-mentioned positive pole 10 can include positive electrode collector and form the positive electrode active material layer on above-mentioned positive electrode collector.
Above-mentioned positive electrode active material layer can include positive active material and adhesive, and can optionally include conductive agent.
As above-mentioned positive electrode collector, aluminium (Al), nickel (Ni) etc. can be used, but be not limited to this.
As above-mentioned positive active material, can use can reversibly make the compound of lithium insertion and deintercalation.It is specific and
In speech, composite oxides or compound phosphoric acid compound that cobalt, manganese, nickel, aluminium, iron or combinations thereof metal and lithium can be used
More than one.More specifically, can use lithium and cobalt oxides, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide,
Lithium nickel cobalt aluminum oxide, lithium iron phosphoric acid compound or combinations thereof.
Above-mentioned adhesive, which is played, not only makes positive active material particle adhere to well each other, and makes positive active material
The effect on positive electrode collector is attached to well, as specific example, there is polyvinyl alcohol, carboxy methyl cellulose, hydroxyl
Propyl cellulose, diacetyl cellulose, polyvinyl chloride, the polyvinyl chloride through carboxylation, polyvinyl fluoride, the polymerization containing oxirane
Thing, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene (PTFE), Kynoar based polymer, polyethylene, polypropylene, styrene-
Butadiene rubber, propylated SBR styrene butadiene rubberses, epoxy resin, nylon etc., but it is not limited to this.They can be single
Solely or mix two or more use.
Above-mentioned conductive agent is used to assign electric conductivity to electrode, as its example, there is native graphite, Delanium, carbon black, carbon
Fiber, metal dust, metallic fiber etc., but it is not limited to this.They individually or can mix two or more use.It is above-mentioned
Metal dust and above-mentioned metallic fiber can use the metals such as copper, nickel, aluminium, silver.
Above-mentioned negative pole 20 can include negative electrode collector and form the negative electrode active material layer on above-mentioned negative electrode collector.
As above-mentioned negative electrode collector, copper (Cu), golden (Au), nickel (Ni), copper alloy etc. can be used, but be not limited to
This.
Above-mentioned negative electrode active material layer can include negative electrode active material and adhesive, and can be optionally comprising leading
Electric agent.
As above-mentioned negative electrode active material, can use can reversibly make lithium ion insert and take off slotting material, lithium gold
Category, lithium metal alloy, lithium can be doped and dedoping material, transition metal oxide or combinations thereof.
It lithium ion is inserted and take off slotting material as above-mentioned, carbon system material can be enumerated, shown as it
Example, can enumerate crystalline carbon, amorphous carbon or combinations thereof.As the example of above-mentioned crystalline carbon, non-setting, plate can be enumerated
Shape, flakey (flake), spherical or fibrous native graphite or Delanium., can be with as the example of above-mentioned amorphous carbon
Enumerate soft carbon (soft carbon) or hard carbon (hard carbon), mesophase pitch carbide, coke through burning till etc..As
Above-mentioned lithium metal alloy, can use lithium and selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba,
The alloy of metal in the group of Ra, Ge, Al and Sn composition.As it is above-mentioned lithium can be doped and dedoping material, can
To enumerate Si, SiOx(0 ＜ x ＜ 2), Si-C complexs, Si-Y alloys, Sn, SnO2, Sn-C complexs, Sn-Y etc., additionally may be used
With by least one in them and SiO2Mix to use.As above-mentioned element Y, can be selected from by Mg, Ca, Sr, Ba, Ra,
Sc、Y、Ti、Zr、Hf、Rf、V、Nb、Ta、Db、Cr、Mo、W、Sg、Tc、Re、Bh、Fe、Pb、Ru、Os、Hs、Rh、Ir、Pd、Pt、
Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po and combinations thereof composition group.
As above-mentioned transition metal oxide, barium oxide, lithium-barium oxide etc. can be enumerated.
The adhesive and the species of conductive agent used in above-mentioned negative pole and the adhesive and conduction used in foregoing positive pole
The species of agent is identical.
Above-mentioned positive pole and negative pole can be manufactured by the following method：Respective active material and bonding are mixed in a solvent
Above-mentioned active compound composition is applied to each by agent and optionally hybrid conductive agent with manufacturing each active compound composition
Collector.Now, above-mentioned solvent can use 1-METHYLPYRROLIDONE etc., but be not limited to this.This electrode manufacturer
Method is the content being widely known by the people in the field, therefore detailed description will be omitted in this manual.
Above-mentioned electrolyte includes organic solvent and lithium salts.
Above-mentioned organic solvent plays the effect of the medium of the ion movement for the electrochemical reaction that can make participation battery.As
Its specific example, can be molten from carbonate-based solvent, ester series solvent, ether series solvent, ketone series solvent, alcohol series solvent and aprotic
Selected in agent.
As the example of above-mentioned carbonate-based solvent, dimethyl carbonate (DMC), diethyl carbonate can be enumerated
(DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethylpropyl carbonate (EPC), ethyl-methyl carbonic acid
Ester (EMC), ethylene carbonate (EC), propene carbonate (PC), butylene (BC) etc..Specifically, when by chain carbonic acid
Ester compounds and cyclic carbonate compound mixing come in use, can produce sticky smaller while dielectric constant is improved
Solvent.Now, cyclic carbonate compound and linear carbonate compound can be by 1:1~1:9 volume ratio is mixed
To use.
As the example of above-mentioned ester series solvent, methyl acetic acid ester, ethylhexoate, n-propyl acetic acid esters, two can be enumerated
Methyl acetic acid ester, methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone (decanolide), valerolactone, mevalonolactone
(mevalonolactone), caprolactone (caprolactone) etc..As the example of above-mentioned ether series solvent, two fourths can be enumerated
Base ether, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxy-ethane, 2- methyltetrahydrofurans, tetrahydrofuran etc..As
Above-mentioned ketone series solvent, can enumerate cyclohexanone etc., as above-mentioned alcohol series solvent, can enumerate ethanol, isopropanol etc..
Above-mentioned organic solvent can individually or mix it is two or more use, mix it is two or more to use when mixing ratio
Rate can suitably be adjusted according to the target of battery performance.
Above-mentioned lithium salts is following material：It can dissolve in organic solvent, and the supply source in battery as lithium ion
The work of basic electrochemical cell is carried out playing a role, promote shifting of the lithium ion between positive pole and negative pole
It is dynamic.
As the example of above-mentioned lithium salts, LiPF can be enumerated6、LiBF4、LiSbF6、LiAsF6、LiN(SO3C2F5) 2、LiN
(CF3SO2)2、LiC4F9SO3、LiClO4、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2) (x and y are natural number),
LiCl、LiI、LiB(C2O4)2Or combinations thereof.
The concentration of above-mentioned lithium salts can be used in the range of 0.1M~2.0M.When lithium salts concentration within the above range
When, electrolyte has appropriate conductivity and viscosity, therefore, it is possible to show excellent electrolyte property, so that lithium ion energy
It is enough effectively to move.
Embodiment
Below by way of description Production Example, embodiment, comparative example and experimental example so as to which the present invention will be described in more detail.
In addition, following Production Examples, embodiment, comparative example and experimental example an only of the invention example, are not construed to this
The content of invention is defined in this.
Production Example 1：The manufacture of macromolecule resin 1
The solution that 28% ammonia spirit of addition in phenolphthalein (100g, 314mmol) is produced is stirred at room temperature 20
My god.When above-mentioned solution turns into substantially transparent, above-mentioned solution is injected into concentrated hydrochloric acid and ice and terminates reaction.Product is steamed
Distilled water is cleaned to after as neutrality, is recrystallized using second alcohol and water, synthesis chemical formula 3-1 compound.By above-mentioned synthesis
Chemical formula 3-1 compound (44.4g, 140mmol) and triethylamine (triethylamine) (35.8g, 350mmol) addition
After into dichloromethane (methylenechloride) (210ml), 0 DEG C is cooled to.Gradually added 28.1g benzene in 1 hour
Base phosphonyl dichloride (phenylphosphonic dichloride (BPOD, benzenephosphorus oxydichloride))
After the solution for being dissolved in dichloromethane (15ml), react 4 hours at room temperature.The solution dilution after terminating will be reacted
HCl solution and distilled water cleaning are for several times.Macromolecule after cleaning is dried 48 hours in 80 DEG C of vacuum constant-temperature containers, weight is obtained
Mean molecule quantity be 125,000g/mol and glass transition temperature be 248 DEG C the repeat unit with chemical formula 6 high score subtree
Fat 1.
[chemical formula 3-1]
[chemical formula 6]
Production Example 2：The manufacture of macromolecule resin 2
The solution for making addition 40% methylamine (methylamine) aqueous solution in phenolphthalein (100g, 314mmol) and producing
Reacted 24 hours at 30 DEG C.Afterwards, above-mentioned solution is injected in concentrated hydrochloric acid and ice and terminates to react.Product is filtered
Afterwards, cleaned, then recrystallized using second alcohol and water with distilled water, synthesis chemical formula 3-2 compound.Make above-mentioned
The chemical formula 3-2 of synthesis compound (46.4g, 140mmol) is reacted under the same conditions with above-mentioned Production Example 1, is obtained
To weight average molecular weight be 138,000g/mol and glass transition temperature be 210 DEG C the repeat unit with chemical formula 7 height
Molecule resin 2.
[chemical formula 3-2]
[chemical formula 7]
Production Example 3：The manufacture of macromolecule resin 3
Make addition aniline (aniline) (300ml, 3287mmol) and aniline hydrochloride in phenolphthalein (100g, 314mmol)
(aniline hydrochloride) (100g, 965mmol) and the solution that produces react 5 hours at 185 DEG C.Afterwards, drop
Low temperature, injects in concentrated hydrochloric acid and ice to above-mentioned solution and terminates to react.After being filtered to product, carried out with distilled water
Cleaning, is then recrystallized using ethanol, synthesis chemical formula 3-3 compound.Make the chemical formula 3-3 of above-mentioned synthesis chemical combination
Thing (55.1g, 140mmol) is reacted under the same conditions with above-mentioned Production Example 1, and it is 148 to obtain weight average molecular weight,
000g/mol and glass transition temperature for 202 DEG C of the repeat unit with chemical formula 8 macromolecule resin 3.
[chemical formula 3-3]
[chemical formula 8]
Embodiment 1：The manufacture (barrier film containing macromolecule resin 1+ inorganic particulates) of barrier film
By the macromolecule resin 1 produced in above-mentioned Production Example 1 so that 10 weight % are dissolved in tetrahydrofuran (THF) and manufacture
Go out polymer solution.Also, by Al2O3(Japanese light metal company system, LS235A) is added to acetone (big well with 25 weight %
King Company's system) in, ground 3 hours at 25 DEG C using ball mill and disperse it, produce inorganic dispersion liquid.It is above-mentioned to produce
The mixed solution of high-molecular resin solution and inorganic dispersion liquid and DMA (DMAc) and THF is with respectively
2.5：5：2.5 weight is stirred 1 hour than being mixed, and using power mixer at 25 DEG C, produces porous heat-resisting
Layer composition.
In thickness it is the porous substrate of 9 μm of polyethylene monofilm by the above-mentioned heat-resisting layer composition of the porous produced
Two sides is respectively applied after the thickness for 1.5 μm with dip coating manner, and it is dried 1 minute at 110 DEG C and barrier film is produced.
Embodiment 2：The manufacture (barrier film containing macromolecule resin 2+ inorganic particulates) of barrier film
In above-described embodiment 1, the macromolecule resin except replacing Production Example 1 using the macromolecule resin 2 of Production Example 2
Outside 1, similarly implement and produce the barrier film that gross thickness is 12 μm.
Embodiment 3：The manufacture (barrier film containing macromolecule resin 3+ inorganic particulates) of barrier film
In above-described embodiment 1, the macromolecule resin except replacing Production Example 1 using the macromolecule resin 3 of Production Example 3
Outside 1, similarly implement and produce the barrier film that gross thickness is 12 μm.
Comparative example 1：The manufacture of barrier film
Except replacing above-mentioned manufacture using poly- (butyl acrylate-co- methyl methacrylate-co- vinyl acetates)
Outside the macromolecule resin 1 produced in example 1, barrier film is produced in the same manner as in Example 1.
Experimental example
Macromolecule resin and comparative example 1 for Production Example 1~3 it is poly- (butyl acrylate-co- methyl methacrylates-
Co- vinyl acetates), determine weight average molecular weight (Mw) and glass transition temperature (Tg) by the following method respectively and fire-retardant
Property, it the results are shown in table 1 below.
(1) weight average molecular weight (Mw)：With the polystyrene conversion numerical value determined by gel permeation chromatography (GPC)
To represent.
(2) glass transition temperature (Tg)：It is measured by differential scanning calorimetry (DSC).
(3) anti-flammability (1/8 ")：It is measured according to the fire-retardant regulations of UL94VB.
[table 1]
For the barrier film produced in 1~embodiment of above-described embodiment 3 and comparative example 1, pass through the measure side of following discloses
Method determines anti-flammability, percent thermal shrinkage and air penetrability, the results are shown in table 2.
Experimental example 1：The measure of anti-flammability
For the barrier film produced in 1~embodiment of above-described embodiment 3 and comparative example 1, pass through method system as described below
Test film is made, anti-flammability is evaluated according to UL94VB fire-retardant regulations.
By the 10cm × 50cm produced in 1~embodiment of embodiment 3 and comparative example 1 barrier film be folded into 10cm ×
After 2cm, fix top and the bottom to manufacture test film.According to UL94VB, anti-flammability grade is using the burning time of test film as base
Standard is measured.
Experimental example 2：The measure of percent thermal shrinkage
In order to which the percent thermal shrinkage to the barrier film produced in 1~embodiment of above-described embodiment 3 and comparative example 1 is measured,
Perform following methods.The each barrier film produced by above-described embodiment and comparative example is cut to wide (MD) 5cm × length (TD)
5cm, produces totally 7 samples.After above-mentioned each sample is taken care of 30 minutes in 200 DEG C of chamber respectively, to the MD of each sample
The shrinkage degree in direction and TD directions is measured, and calculates percent thermal shrinkage.
Experimental example 3：The measure of air penetrability
The air penetrability of the barrier film to being produced in 1~embodiment of above-described embodiment 3 and comparative example 1 is carried out by the following method
Determine：Using EG01-55-1MR (Asahi Seiko company systems), 100cc air is surveyed by the time needed for barrier film
It is fixed.
[table 2]
| The anti-flammability of barrier film | Air penetrability (sec/100cc) | Shrinkage factor (%) | |
| Embodiment 1 | V0 | 220 | Less than 1 |
| Embodiment 2 | V0 | 240 | Less than 1 |
| Embodiment 3 | V0 | 250 | Less than 1 |
| Comparative example 1 | V2 | 255 | 55 |
Referring to above-mentioned table 2, using the macromolecule resin comprising the first component and the second component, (wherein the first component contains
Phosphonate, the second component contains nitrogen) manufacture during barrier film, excellent in flame retardance reaches V0.And confirm that percent thermal shrinkage is less than
1%, and air penetrability is below 250sec/100cc.
Specific part of the invention described in detail above, but for the personnel with general knowledge in terms of this area
Speech, it is clear that this specific description is only preferred embodiment, not limits the scope of the present invention with this.It therefore, it can
Say that the essential scope of the present invention is defined by claim and its equivalent.
Claims (14)
1. a kind of barrier film, including：
Porous substrate；With
Porous refractory layer, is formed at the one or both sides of the porous substrate,
The porous refractory layer includes macromolecule resin, and the macromolecule resin is included containing the first component and the second component
Repeat unit,
First component contains phosphate or phosphonate,
Second component contains nitrogen.
2. barrier film according to claim 1, wherein, first component includes following chemical formula 1 or following chemical formula 2,
Chemical formula 1:
Chemical formula 2:
In the chemical formula 1 and chemical formula 2, R1And R2It is separately hydrogen, or selected from by substituted or non-substituted C1-6
Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-20Cycloalkyl and C6-30Aryl composition group.
3. barrier film according to claim 1, wherein, second component includes acid imide or amide groups.
4. barrier film according to claim 3, wherein, the acid imide includes phthalimide.
5. barrier film according to claim 1, wherein, second component includes following chemical formula 3,
Chemical formula 3:
In the chemical formula 3, R3For hydrogen, or selected from by substituted or non-substituted C1-6Alkyl, C2-6Alkenyl, C2-6Alkynes
Base, C3-10Cycloalkyl and C6-30Aryl composition group.
6. barrier film according to claim 1, wherein, the repeat unit is in following chemical formula 4 and following chemical formula 5
Any one repeat unit,
Chemical formula 4:
Chemical formula 5:
In the chemical formula 4 and chemical formula 5, R1~R3It is separately hydrogen, or selected from by substituted or non-substituted C1-6
Alkyl, C2-6Alkenyl, C2-6Alkynyl, C3-20Cycloalkyl and C6-30Aryl composition group.
7. barrier film according to claim 1, wherein, the glass transition temperature of the macromolecule resin is 180 DEG C~300 DEG C.
8. barrier film according to claim 1, wherein, the porous refractory layer further polymerize comprising Kynoar system
Thing.
9. barrier film according to claim 1, wherein, the porous refractory layer further contains inorganic particulate.
10. barrier film according to claim 9, wherein, the inorganic particulate, which is included, to be selected from by Al2O3、SiO2、B2O3、Ga2O3、
TiO2And SnO2One or more of group of composition.
11. barrier film according to claim 10, wherein, the content of the inorganic particulate is relative to the porous refractory layer
The gross weight of overall solid constituent is the weight % of 70 weight %~98.
12. a kind of manufacture method of barrier film, including：
The heat-resisting layer composition of the porous containing macromolecule resin and solvent is manufactured, the macromolecule resin, which is included, contains first group
Divide the repeat unit with the second component, first component contains phosphate or phosphonate, and second component contains nitrogen；
The heat-resisting layer composition formation porous refractory layer of the porous is utilized in the one or both sides of porous substrate.
13. a kind of electrochemical cell, including positive pole, negative pole, barrier film and electrolyte, wherein, the barrier film is claim 1~11
In any one described in barrier film.
14. electrochemical cell according to claim 13, wherein, the electrochemical cell is lithium secondary battery.
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| KR1020140110953A KR101709695B1 (en) | 2014-08-25 | 2014-08-25 | Heat-resistant, nonflammable, coated separator and battery |
| KR10-2014-0110953 | 2014-08-25 | ||
| PCT/KR2015/008656 WO2016032166A1 (en) | 2014-08-25 | 2015-08-19 | Separator membrane having high heat resistance and flame retardancy, and electrochemical battery |
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| CN111052446A (en) * | 2017-11-29 | 2020-04-21 | 松下知识产权经营株式会社 | Nonaqueous electrolyte secondary battery |
| CN111916637A (en) * | 2020-07-31 | 2020-11-10 | 江苏厚生新能源科技有限公司 | Polyolefin microporous membrane with flame-retardant coating, preparation method thereof and lithium battery |
| CN112234259A (en) * | 2020-01-06 | 2021-01-15 | 蜂巢能源科技有限公司 | Battery cell manufacturing method and lithium ion battery |
| CN112331856A (en) * | 2020-11-03 | 2021-02-05 | 华东理工大学华昌聚合物有限公司 | Lithium ion battery electrode binder and preparation method and application thereof |
| CN113991172A (en) * | 2021-09-30 | 2022-01-28 | 中国地质大学（武汉） | Linear single-ion conductive polymer electrolyte PECB and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101709695B1 (en) | 2017-02-24 |
| KR20160025079A (en) | 2016-03-08 |
| JP6657185B2 (en) | 2020-03-04 |
| CN107004806B (en) | 2020-03-20 |
| WO2016032166A1 (en) | 2016-03-03 |
| JP2017529657A (en) | 2017-10-05 |
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